Finding the Transition State of Quasi-Barrierless Reactions by a Growing String Method for Newton Trajectories: Application to the Dissociation of Methylenecyclopropene and Cyclopropane
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- 作者：Wolfgang Quapp ; Elfi Kraka ; Dieter Cremer
- 刊名：Journal of Physical Chemistry A
- 出版年：2007
- 出版时间：November 8, 2007
- 年：2007
- 卷：111
- 期：44
- 页码：11287 - 11293
- 全文大小：288K
- 年卷期：v.111,no.44(November 8, 2007)
- ISSN：1520-5215
文摘
A method for finding a transition state (TS) between a reactant minimum and a quasi-flat, high dissociationplateau on the potential energy surface is described. The method is based on the search of a growing string(GS) along reaction pathways defined by different Newton trajectories (NT). Searches with the GS-NT methodalways make it possible to identify the TS region because monotonically increasing NTs cross at the TS or,if not monotonically increasing, possess turning points that are located in the TS region. The GS-NT methodis applied to quasi-barrierless and truly barrierless chemical reactions. Examples are the dissociation ofmethylenecyclopropene to acetylene and vinylidene, for which a small barrier far out in the exit channel isfound, and the cycloaddition of singlet methylene and ethene, which is barrierless for a broad reaction channelwith Cs-symmetry reminiscent of a mountain cirque formed by a glacier.